O-hydrocarbon, s-(quaternary ammonium-substituted alkyl) esters of phosphorothioic acids and insecticidal compositions thereof



O-HYDROCARBON, S-(QUATERNARY AMMONI- UM-SUBSTITUTED ALKYL) ESTERS F PHOS- PHOROTHIOIC ACIDS AND INSECTICIDAL COMPOSITIONS THEREOF Jack A. Snyder, Claymont, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application January 31, 1958 Serial No. 712,310

Claims. (Cl. 167-22) X is oxygen or sulfur R is hydrocarbon radical of less than 8 carbon atoms R is an alkylene radical of 2 to 4 carbon atoms R R and R are the same or different and are hydrocarbon radicals of less than 8 carbon atoms with the proviso that R, and R can be taken together to form, with the nitrogen atom between them, a heterocyclic group A is an anionic salt-forming group More particularly the compounds of the invention are those of Formula 1 where:

X is selected from the group consisting of oxygen and sulfur R is selected from the group consisting of alkyl radicals of from 1 to 4 carbon atoms, inclusive, alkenyl of 2 to 4 carbon atoms, benzyl, phenyl, halophenyl, nitrophenyl, and tolyl radicals R is an alkylene radical of from 2 to 4 carbon atoms R, is selected from the group consisting of alkyl radicals of from 1 to 4 carbon atoms, inclusive, and alkenyl radicals of 2 to 4 carbon atoms R and R are the same and are alkyl radicals of from 1 to 4 carbon atoms, inclusive, or alkenyl radicals of 2 to 4 carbon atoms with the proviso that they can be taken together to form, with the included nitrogen, the pyrrolidine, piperidine, piperazine and morpholine rings .A is selected from the group consisting of halogen, alkyl sulfate of from 1 to 4 carbon atoms, inclusive, benzenesulfonate, and toluene-sulfonate From the above, it will be seen that the compounds of the invention can be named generically as salts of O-hydrocarbon, S-(quaternary ammonium-substituted 2,922,739 Patented Jan. 2%, 1960 secticide are used herein in their broad common usage to include spiders, mites, ticks, and like pests which are not in the strict biological sense classed as insects. Thus, the usage herein conforms to the definitions provided by Congress in Public Law 104, the Federal Insecticide, Fungicide, and Rodenticide Act of 1947, Section 2, Subsection h, wherein the term insect is used to refer not only to those small invertebrate animals belonging mostly to the class Insecta, comprising six-legged, usuallywinged forms, as beetles, bugs, bees, flies, and so forth, but also to other allied classes of arthropods whose members are Wingless and usually have more than sin legs, as spiders, mites, ticks, centipedes and wood lice,

The compounds of the invention are readily prepared as illustrated by the following equations showing specific reactants:

( (EH50 O CQHH PS-CH2CH2-N (CH3)2SO4 HO CzHs starting material SCHzCHr- CHaSOi HO C2 5 The preparation of the starting materials of Equation 2 and analogs thereof, all of which can be used as intermediates in preparing compounds of the present invention, are disclosed and claimed in my copending application, Serial No. 495,321, wherein detailed methods for their preparation are set forth. Briefly, the formation of the above starting material is described by the following equation:

This may be broken down into. the following steps, which occur consecutively to give the overall reaction above.

(a) CONDENSATION S 2 6 )2POCHzOHz (C2 5): A' sM (b) ISOMERIZATION This isomerization is noted by R. Ghosh and J. F. Newman, Chem. and 1nd, Jan. 29, 1955, p. 118, for the above compound, and is further. described for this compound by T. R. Fukuto and E. M. Stafford, J. Am. Chem. Soc. 79, 6083 (1957). t

There are vague literature references to this type of reaction, although it has remained for me to show the specificity of the cleavage of O-alkyl groups from O,S-dialkyl phosphate esters by trialkylamine hydrochlorides or lithium chloride.

V. M. Clark and A. R. Todd, J. Chem. Soc., 2023 (1950), ibid., 2030 (1950), describe the cleavage of henzyl groups (very easily removed) from phosphate esters with'amine salts and inorganic salts.

I. Lecocq and A. R. Todd, J. Chem. Soc., 2381 (1954), describe the cleavage of lower alkyl groups from thiolphosphate esters having electron-withdrawing groups such as phenyl, using lithium chloride.

L. Zervas and I. Dilaris, J. Am. Chem. Soc. 77, 5354 (1955 have shown the cleavage of allryl groups from trialkyl phosphates, using sodium or barium iodide, stronger reagents than amine hydrochlorides or lithium chloride.

Perhaps the most pertinent of these is the second reference. None of these authors tried cleaving mixed O-alkyl, S-alkyl esters. If they had, they would have found that possession of an S-alkyl group activates the ester so that amine hydrochlorides or lithium halides can cleave an O-alkyl. The cleavage is illustrated'by the following reactions which I have carried out:

The peculiar influence of the S-alkyl group is confirmed by:

CzHsO S PO 02115 LiGl 100 22 hrs.

-r ethylene glycol monoeth lether crrno y No reaction. Beactant recovered and identified.

This cleavage reaction also operates where the S-alkyl activating group is S-(2-diethylaminoethy1-) in Reaction 0. Here, also, an O-ethyl is cleaved.

Therefore, the Reaction 3 given, by which the intermediate arises, is a shorthand form of the situation expressed in the sequence (a)- (b)+ (c). I have indicated this by synthesizing the product of (b) and cleaving it with triethylamine hydrochloride in ethylene glycol, monoethyl ether to give a product identical with the product of Reaction 3-.

It may thus be seen that an alternative method to the useof the reaction of Equation 3 for preparing the starting material is Equation 0. Preparation of the trialkyl ester used as starting material in Reaction c is described in the Fukuto and Stafford reference given above.

The reaction of Equation 3 above is preferably carried out in an inert organic solvent such as benzene, chlorobenzene, toluene, xylene, octane, tetrahydrofuran and the like and is speeded by heating, say at reflux temperature. An acid-accepting amine such as triethylamine is used in the process.

The alternative Reaction 0 above is preferably carried out in an inert organic solvent such as those given above, or more preferably an ethylene glycol, monoalkyl ether, using an amine hydrochloride such as trimethylamine hydrochloride or triethylam-ine hydrochloride or by using an alkali metal halide, preferably lithium chloride. The reaction is speeded by heating.

The reaction of Equation 2 above is preferably carried out inan inert organic solvent such as benzene, toluene, xylene, dialkyl ether, tetrahydrofuran, chloroform, carbon tetrachloride and the like. It ordinarily proceeds at room temperature but elevated temperatures can be used if desired. r

In order to use the compounds of the invention to best advantage as insecticides, they are formulated with an inert carrier, such material sometimes also being referred to in the art as a modifier or conditioning agent or in.

some cases a diluent or extender. Such formulation is desirable in order to provide compositions adapted for ready and eflicient application to insects or loci to be protected therefrom using conventional applicator equipment. Thus the compounds are formulated in compositions which take the form of solutions, dusts, water-dispersible powders, emulsions, aerosols and the like. They can also be used in insect baits in the form of a dispersion on a dry carrier with an attractant or in the form of a syrup.

By the term inert carrier, I mean a substance which is capable of presenting or. aiding in the presentation of an active compound to an insect. The term carrier" is well established in the 'art where it is recognized that an active agent or toxicant is in itself of little practical utility for combating insects unless it .be presented in a form suitable for effecting intimate contact of the agent or its vapors, as the particular case may require, .Wlllh the insect. Thus additional material or materials are employed in formulating at least one activeagent of Eormula l to yield a suitable insect control composition, such materials being ad juvants.

Suitable inert carriers that can be used in the compositions include wetting, dispersing, andemulsifying agents set out in US. Patent 2,655,445 can be employed in pre paring the pest control compositions of the present invention. Other suitable wetting, dispersing and emulsifying agents such as those listed in detail in articles by Me- Cutcheon in Soap and Sanitary Chemicals, August, September, and October of 1949 can also be used. Preferably, however, the wetting, dispersing or emulsifying agents used in the pest control compositions of the invention are of the cationic and nonionic types.

Compositions of the invention are usually first prepared in the form of concentrates suitable for solution or dispersion in water to give aqueous spray compositions. The compounds of the invention are generally water soluble and suitable concentrates can therefore be prepared by admixing a wetting, dispersing, or emulsifying agent with one or more of the compounds ofForula l in otherwise undiluted form. Although the wetting, dispersing, or emulsifying agent can be used in large amounts, say up to 50 percent or more of the formulation, ordinarily it will not comprise more than 20 percent by weight of the formulation, and with the better of such adjuvant materials the percentage will be 5 percent or less.

Dust compositions of the invention contain one or more compounds of Formula 1 admixed with or adsorbed on finely divided carriers or dusts-such as talc, pyrophyllite, natural clays, diatomaceous earths, and other powdered diluents such as those set out in the aforementioned U.S. patent. The. dust compositions are prepared by intimately mining the compounds of Forumla 1 with a powdered carrier.

Because the compounds of the invention are in general viscous liquids, the manimum concentration of such compounds in a dust composition or water soluble powder of the invention will, of course, vary with the adsorptivity of the particular powder diluent used. For example, if fullers earth is used, the dust may contain as much as about 25 percent by weight of a liquid compound of the invention. Using a less adsorptive diluent such as pyrophyllite, however, it is necessary to reduce the content of liquid compound appreciably in order to obtain a free-flowing powdered pest control composition.

Preferred water-dispersible powders of the invention contain of the order of about 25 percent or less by weight of a compound of the invention dispersed on a highly adsorbent inert powdered diluent such as fullers earth or diatomaceous earth. Such water-dispersible powders can also contain aneffective amount of a dispersing or emulsifying agent. Usually such powders will contain less than 10 percent by weight of the dispersing oremlusifying agent. I

In actual application of the compositions for insect control, it is generally preferred that the active compound or compounds be present in relatively low concentrations. Thus, the concentrates are dissolved or dispersed in water to obtain aqueous compositions suitable concentration for practical application.

In applying the compounds of the invention forinsect control, the compound is, of course, applied in amount suflicient to exert the desired insecticidal action. The amounts required, however, to give insecticidal action are extremely small because of their unusual eflectivenms.

The compounds are applied to the locus or area to be protected. Such application can be made directly upon the locus or area and the insects thereon during the period of infestation or, alternatively, the-application can be made in advance of an anticipated insect infestation or otherwise applied so that the insects will come into contact with the active compound and be killed.

The compositions of the invention can include fungicides such as zinc dimethyldithiocarbamate, zinc ethylene bis-dithiocarbamate and manganese ethylene bis-dithiocarbamate, insecticides such as DDT, methoxychlor, chlordane, parathion, EPN, dieldrin, aldrin and malathion, and other fungicides and insecticides such as those set out in U.S. Patent 2,426,417.

In order that the invention may be better understood, the following additional examples are given. Because standard rules for naming many types of org-anophosphorus compounds have not been set forth by the various organizations which establish the rules of chemical nomen clature, the naming system used here will be described.

A hypothetical hydrolysis of the compound as performed at the site of the SC bond. The quaternarysubstituted alcohol which results is then named. To describe the compounds of the invention it is only necessary to give the name of the quaternary-substituted alcohol and to state that the compounds are S-esters of that alcohol with the phosphorothioic or phosphorodithioic acid moiety obtained in the hydrolysis (321150 0 OH; hypothetical e hydrolysis P' SCHQCHQN GZH5 CH3S 04 H O oa a diethyl (2-hydroxyethyl)methylammonium methyl sulfate, S-ester with phosphorothioic acid, O-ethyl ester CzHsO 0 CH3 e P--SH HOCHrCH-N-CzEs CHaSOt Phosphorothioic Diethyl (2-hydroxyethyl)methylacid O-ethyl ester Phosphorothioic acid, O-ethyl, S-(Z-diethyl amino- I ethyl)ester, a starting material used in the preparation of the compound of this example, is first obtained as follows:

METHOD OF EQUATION 3 with drying tube. It was then cooled to room temperature and filtered. The crystals were washed with two SO-ml. portions of benzene and sucked dry. The yield was 35 g., 51 percent, calculated as triethylamine hydrochloride. The filtrate andwashings were combined and extracted -with two 100-ml. portions of water. The water extracts were combined and extracted with two 100-ml. portions of nitromethane. A 20.8 g. portion of the sample was dissolved in 50 ml. of water (pH 6) and passed over a column of Amberlite IR4B ion-exchange resin, the first 30 m1. of effluent, column holdup, being discarded. The efiluent (pH 8).was collected, volume 100 ml. This was passed over Amberlite IRC50 resin, 30 ml. being discarded, and 150 ml. (pH 2) being collected. This was again passed over IR4B resin, 30 ml. being discarded and 200 ml. (pH 6-7) being collected. This solution was concentrated to a thick, light yellow sirup in vacuo (90 bath), and dried by heating /2 hr. at 90/0.1 mm. The yield was 14.2 g., 68 percent. Sulfur, nitrogen and phosphorus were present; halogen was a-bsent.

Calcd. for: C N NO PS: C, 39.8; H, 8.36. Found: C, 39.3; H, 8.65.

METHOD OF EQUATION 0 A solution of 6.72 g., 0.025 mole, of phosphorothioic acid, 0,0-diethyl, S-(Z-diethylaminoethyl)ester (see Fukuto and Staiford reference), 10.25 g., 0.075 mole, of triethylamine hydrochloride, and 50 ml. of ethylene glycol, monoethyl ether was heated at 100 on a steam bath in a 100 ml. round-bottom flask with condenser and drying tube for 6 hrs. It was then allowed-to cool to room temperature and stand overnight. The crystals were filtered, washed with 50 ml. of ether, sucked dry, and air-dried for 1 hr. The yield was 5.73 g., M.P. 221- 235 (uncorr.), impure triethylamine hydrochloride. The filtrate, 55 ml., and washings (diluted to 55 ml. with ether) were combined and allowed to stand 15 min. at room temperature. The crystals were filtered, washed with 50 ml. of ether, sucked dry, and air-dried A: hour. The yield was 2.71 g., M.P. 201-218 (uncorr.). The filtrate and washings were combined and concentrated to a sirup in vacuo (90 bath). This amounted to 7.26 g. after drying 15 min. at 90/O.1 mm. It was dissolved in 50 m1. of water and extracted with two 50-ml. portions of nitromethane. The water layer was concentrated to a sirup in vacuo (90 bath) and dried 15 min. at 90/0.1 mm. The yield was 4.85 g., percent. This was dissolved in 25 ml. of water and passed over Amberlite IR4B ion-exchange resin (efiiuent pH 8), IRCSO resin (efiluent pH 2) and IR4B- resin (efliuent pH 7) in exactly the same procedure as used in the above procedure except for adjusting effiuent volumes for the sample volume used. The final efiluent was concentrated to a sirup in vacuo bath), which was dried by heating 15 min. at 90/0.1 mm. The yield was 2.96 g., 61 percent. The infrared spectrum was found to be qualitatively identical with that of the product of the above procedure.

Calcd. for C H NO PS: C, 39.8; H, 8.36. Found: C, 39.5; H, 8.69.

The product of either of the above procedures was then quaternized as in Reaction 2 in the following manner:

A mixture of phosphorothioic acid, O-ethyl, S-(2-diethylaminoethyl)ester, 3.25 g., 0.0135 mole, prepared asv above, redistilled dimethyl sulfate, 1.70 g., 0.0135 mole, and 25 ml. of dry benzene was shaken mechanically for 6 hrs. and then allowed to stand 24 hrs. at room temperature. Two layers formed. The mixture was shaken vigorously, poured into a small separatory funnel, and the lower layer was drawn oil. This was freed of residual benzene by heating at 50/ 0.1 mm. for /2 hr. The yield was 3.40 g., 69 percent, of a light brown, viscous sirup.

Calcd. for C H NO PS C, 32.7; H, 7.13, Found; C, 33.5; H, 7.26.

Wave Length In Microns Relative Band in medium. weak, broad.

. very weak, side band broad.

very weak, broad.

' medium, broad.

w e -1 strong. strong, broad. weak. very weak. very strong.

. very weak.

very weak, broad. very weak, broad. str n tb t very wealg'broad.

EXAMPLE 2 Preparation of diethyl (Z-hydroxyethyl)methyl-ammonium p-toluene sulfonate, S-e'stef with p'hosphorothioic acid, O-ethyl ester EXAMPLE 3 Preparation tririiie thyl (Z-hydroxyethyl)ammounium iodide, S-ester with phosphorothioic acid, O-ethyl ester ozngo o /OHa r-s-cm-cnrii ons 1- HO CH3 A mixture of 5 parts by weight of phosphorothioic acid O-e'thyl, S-(2-dimethylaminoethyl) ester, and 10 parts by weight of methyl iodide is heated at 50 C. for 14 hours in a sealed vessel. After cooling the contents of the vessel to room temperature, the vessel is opened and heated to 50 C. whereupon excess methyl iodide vaporizes and is removed. The desired product remains in the reaction vessel. If it is to be used for pest control purposes, it is not necessary that it be refined further.

EXAMPLES 4 THROUGH 44 02,550 0 CH: Using the general procedures outhned lIl Examples 1,

\T s 2 and 3, supra, the following examples of the prepara- 05s GH3 tion of compounds of this invention are given in tabular HO 02115 form. After reaction under the conditions described is A mixture of phosphorothioic acid, O-ethyl; Si-(Z-di- 30 carried out, the product remains in substantially pure ethylaminoethyDester, prepared as above (see Exar'n ple condltion. If the product is to be used as an insecticide, 1), 3.00 g., 0.0128 mole; methyl p-toluenes'ulfdnate', 2.48 his not necessary to refine it further.

Ex. No. Starting Material Quaternizing Agent stem Product 4 Phosphorodithioic acid, O-eth'yl, S- Dimetbyl's'ultatc, 12.6 parts.. Benzene, 50 parts Diethy l (Z-hydroxyethyl) m'ethylam- (zdiethylaminoethyl) ester, 25.7 momum methyl sulfate, S-es ter with parts. phosphorodithioie acid, O-ethyl ester.

There'sction mixture is'sh'alien i i hrs aii' room temp. The benzene is removed by distillation in Vacuo 5 Phosphorothioic acid, 0 -ethyl, s- Dithylsufiate,15.4'parts... Benzene, so'parts Trietbyl (Z-hydroxyethyl) ammonium (2-diethylaminoethyl) ester, 241 ethylsuifate, S-ester w th phosphorparts. othioic acid, O-ethyl ester.

The reaction mixture is stirred and heated 8.5 hrs. at 50. The benzene is removed by distillation in vacuo 6 1 Phosphorodithioic acid, Q-ethyl, S- Diethyl suliate,'1 5 .4 parts.-. Toluene, 50 parts; Triethyl (2-hydroxyethyl) ammonium (2 diethyla'minoethyl) ester, 2517 etbylsulfate, S-ester with phosphorpa'rts. odithioic acid, O-ethyi ester.

The react-ionmixture is stirredand heated 8.5 hrs. at 50. The toluene is removed by distillation in vacuo 7 .Phosphorodithioic acid, O-ethyl, S- .Methylpetoluene-sulfonate, Chloroform, 50 parts Diethyl ,(2-hydroxyethyl) methylam- (2diethylaminoethy1) ester, 25.7 18.6 parts. monium p-toluenesulfonate, S-ester parts. with phosphorodithioic acid, O-ethyl ester.

The reaction mixture is shaken 86'hrs. at room temp. The chloroform is removed by distillation in vacuo 8 Phosphorothioic acid, OrQthYl, S- Ethyl ytplnene-sulionate, Chloroiorm, 50 parts Triethyl (2hydroxyethyl) ammonium (2-diethylaminoethyl) ester, 24.1 20.0 parts. p-toluenesulfonate, S-ester with phosparts. phorothioic acid, O-ethyl ester.

The reaction mixture is reflu'iied li hrs. The chloroform is removed by distillation in vacuo 9 Phosphorodithioic acid, O-ethyl, S- Ethyl p tolue'nesulfonate, Toluene, 50 parts Tricthyl (2-hydroxyethyl) ammonium (Z-Qiethylaminoethyl) ester, 25.7 20.0 parts. p-toluenesulfona te, S-esterw1th phosparts. phorodithioic acid, O-ethyl ester.

Reaction mirtur'e is stirred and heated '11 hrs. at 50. The toluene is removed by distillation in vacuo 10 Phosphorothioic acid, Oe'tliyl, S'- Meth'yl benz'enesulfonate, Diethyl ther, 50 parts..'..- Diethyl (2-hydroxyethyl) methylani- (2'diethylaminoethyl) ester, 24.1 17.2 parts. momum benzenesirlionate, s ester parts. witth phosphorothioic acid, O-ethyl es er.

Reaction mixture is shaken 36 at ro o'm' was. The ether isremovcd by evaporation in a stream of dry air Ex. No. Starting Material Quaternizing Agent Solvent Product 11 Phosphorodithioic acid, O-ethyl, 8- Methyl benzenesulfonate, Dibutyl ether, 50 parts. Diethyl (2-hydroxyethyl) methylam- (2-dtiethylamineethyl) ester, 25.7 17.2 parts. momum benzenesulfonate, S-ester par s.

with phosphorodithioic acid, O-ethyl esterl Reaction mixture is stirred and heated 3 hrs. at 0.' The dibutyl ether is removed by distillation in vacuo yl (2diethylaminoethyl) ester, '24.1 parts.

No solvent".-.

Phosphorothioic acid, O-ethyl, S- Ethyl benzenesulfonate, Peroxide-free tetrahydro- Triethyl (2-hydroxyethyl) ammonium (2-diethylaminoethyl) ester, 24.1 18.6 parts. furan, 50 parts. benzenesulfonate, S-ester with phosparts. V phorothioic acid, O-ethyl ester.

Reaction mixture is refluxed 4.5 hrs. The tetrahydrofuran is removed by distillation in vacuo 13 Phosphorodithioic acid, O-ethyl, S- Ethyl benzenesulfonate, Benzene, 50 parts Triethyl (2-hydroxyethyl) ammonium (2-diethylaminoethyl) ester, 25.7 18.6 parts. benzenesulionate, S-ester with phosparts. phorodithioic acid, O-ethyl ester.

The reaction mixture is refluxed 2 hrs. The benzene is removed by distillation in vacuo 14..-.-. Phosphorothioic acid, O-ethyl, S- Dimethyl sulfate, 12.6 parts. Carbon tetrachloride, 50 Trimethyl (2-hydroxyethyl) ammo- (2-dimethylaminoethyl) ester, 21.3 parts. nium methyl sulfate, S-ester with parts. phosphorothioic acid, O-ethyl ester.

The reaction mixture is refluxed 1 hr. The carbon tetrachloride is removed by distillation in vacuo 15 Phosphorodithioic acid, O-ethyl, S- Dimethyl sulfate, 12.6 parts. Toluene, parts Trimethyl (2-hydroxyethyl) ammo- (2-dimethylamin0ethyl) ester, 22.9 nium methyl sulfate, S-ester with parts. phosphorodithioic acid, O-ethyl ester.

The reaction mixture is refluxed 10 min. The toluene is removed by distillation in vacuo 16 Phosphorothioic acid, O-ethyl, S- Diethyl sulfate, 15.4 parts.-. Chloroform, parts Dimethyl (2-hydroxyethyl) ethylam- (2-dimethylaminoethyl) ester, 21.3 monium ethyl sulfate, S-ester with parts. phosphorothioic acid, O-ethyl ester.

The reaction mixture is refluxed 4.5 hrs. The chloroform is removed by distillation invacuo 17 Phosphorodithioic acid, O-ethyl, S- Diethyl sulfate, 15.4 parts.-. Xylene, 50 parts Dimethyl (2-hydroxyethyl) ethylam- (2-dimethylaminoethyl) ester, 22.9 monium ethyl sulfate, S-ester with parts. phosphorodithioic acid, O-ethyl ester.

The reaction mixture is stirred 48 hrs. at room temp. The product is extracted with water which is removed by distillation in vacuo 18 Phosphorodithioic acid, O-ethyl, S- Methyl iodide, 282 parts. No solvent"--. Trimethyl (Z-hydroxyethyl) ammo- (2-dimethylaminoethyl) ester, 22.9 nium iodide, S-ester with phosphorparts. odithioie acid, O-ethyl ester.

The reaction is carried out as in Example 3 19 Phosphorothioic acid, O-eth 5- Methyl chloride, 6.30 parts.-

Diethyl (2-hydroxyethyl) methylammonium chloride, S-ester with phosphorothioic acid, O-ethyl ester.

The reactants are combined at 40 in a sealed vessel. This is heated 4 hrs. at 90 cooled to -40, the vess ride is allowed to vaporize on warming to room temp.

el is opened, and the excess methyl chlo- 20 Phosphorodithioic acid, O-ethyl, S- Methyl chloride, 6.30 parts. No solvent Diethyl (2hydroxyethyl) methylam- (2-diethylaminoethyl) ester, 25.7 monium chloride, S-ester with phosparts. phorodithioic acid, Oethyl ester.

The reaction is carried out as in Example 19 21 Phosphorothioic acid, O-ethyl, 8- Methyl bromide, 11.9 parts.. No solvent Diethyl (2-hydroxyethy1) methylam:

24.1 monium bromide, S-ester with phos- (Z-diethylamiuoethyl) ester, parts. v

phorothioic acid, O-ethyl ester.

allowed to vaporize on warming to room temp.

, the vessel is opened, and the excess methyl bromide is Phosphorodithioic acid, O-ethyl S- Methyl bromide, 11.9 parts.. No solvent"-. Diethyl (2hydroxyethyl) methylam- (2-diethy1aminoethyl) ester, 25.7 monium bromide, S-ester with phosparts. phorodithioic acid, O-ethyl ester.

The reaction is carried out as in Example 21 23 Phosphorothioic acid, O-ethyl, S- Ethyl chloride, 8.05 parts No solvent Triethyl (2-hydroxyethyl) ammonium. (2-diethylaminoethyl) ester, 24.1 V chloride, 'S-ester with I parts.

othioic acid, O-ethyl ester.

The reaction is carried out as in Example 21, except that the sealed vessel isheated 5.5 hrs. at

phosphor- V Ex. 1G0 Starting Mada a1 Quaterhizing Ageiii Solvent Product 24 Phosphorodithioic acid, d-etlfil, srole chloride, r165 pee No solvent 'rriern 1 (2-hydroxyethyl) ammonium (2-diethylaminoethyl) ester, 25.7 chloride, 7, S-ester with phosphor: parts. odithioic acid, O-ethyl ester.

The reaction is carried out as in Example 23 25 Phosphorothioic ac'd O-ethyl, HS lithyl bromide, 13.7 parts. Diethyl ether, 50 parts Triethyl (Z-hydroxyethyl) ammonium (Z-diethylaminoethyl) ester, 24.1 bromide, Sester with phosphorparts. othioic acid, O-ethyl ester.

The reaction mixture is stirred and refluxed 45 hrs. The solvent and excess ethyl bromide are removed by concentration in vacuo 26 Phosphorodithioic .acid, rethyl ds Ethyl hromide, 13.7 parts Diethyl ether, 50 parts Triethyl (-2-hydroxyethyD-ammonium (Z-diethylaminoethyl) ester, 25.7 bromide, S ester with phosphor parts. odithioic acid,- O-ethyl ester.

The reaction is carried out as in Example 25 27 Phosphorothioic acid, O-ethyl, Ethyl iodide, 81.0 parts. No solvent Triethyl (2-hydroxyethyl)ammonium (z diethylaminoethyl) ester, 24.1 iodide, S-ester with phosphorothioic parts. acid; O-ethyl ester;

The reactants are combined and refluxed 4 hrs. The excess ethyl iodide is evaporated in a stream of dry air after cooling to roomtemp.

28 Phosphorodithioic acid, O-ethyl,- S liithyl iodide, 31.0 parts No solvent Triethyl (2-hydroxyethyl) ammonium (Z-diethylaminoethyl) ester, 25.7 V iodide, S -ester with phosphorodi-- parts. thioic acid, O-ethy'l ester.

The reaction is carried out as in Example 27 29 Phosphorothioic acid, O-methyl fl bimethylsuliate, 12.6 parts. Benzene, 50 parts Trimethyl (2-hydroxyethyl) ammo: (Z-djmethylaminoethyl) ester, 19.9 v nium methyl sulfate, S-ester with parts. phosphorothioic acid, O-methyl ester.

The reaction mixture is stirred and heated 2 hrs. at 60. The benzene is removed by distillation in vacuo 30 Phosphorothioic acid, O-(sec.-butyl), bibutyl sulfate, 21.0 parts Toluene, 50 parts Diallyl (2-hydroxyethyl)- butylammo- S-(Z-diallylaminoethyl) ester, 29.3 nium butyl sulfate, S-ester with parts. phosphorothioic acid, O (scc.'-butyl) ester.

The reaction mirrors is s tirre'd are tested Zlirs. at The toluene is removed hy distillation in vacuo 31 l liosphorodithioic acid. Oi-{imethyl- V irop yl henzenesulfonate, liexane, 60 parts Diisohutyl (Q-hydroxyethyl) propylallyl), S-(Z-diisobirtylaminoethyl) 20.0 parts; ammonium henrenesulfonatc, S-este'r ester, 33.9 parts; with phosphorodithioic acid, 0-(2- methylallyl) ester.

The reaction mixture is stirred and Fefliiridi his. The hexane is removed by evaporation in a stream of dry air 32--.--- Phos'r'ihorothioic Eaia, o-isdiim i, s- Allyl t miienesuironate, Benzene, 50 parts Dimethyl aiiiydr'p'xprefig'ri 'allylnni: (B-dimthjrl'diuindfiriifitliester, 24.1 21.2 parts. monium o=toluenesulionato, S-ester parts. with phosphorothioic acid, O-isopropyl ester.

The reaction mixture is stirred and'heated 36 hrs. at The benzene is removed by distillation in vacuo 33 Phosphorodithioio acid, Q henzyl, s- Methyl calories, 6.30 parts-Q- No solvent Trimethyl (4-hydroxyb'utyl) ammo i-diinetliylaminoliutyl) ester, 31.9 nium chloride, S=ester with phosparts. phorodithioic acid, O-henzyl ester.

The reaction is carried out a in Example 19 34 Phosphorothioi'c acid, O-plienyl-, S- Propyl-bromid'eflid parts- Benzene, parts- Dimethyl. (Ii-hydroiy-iZ-riiethylpropyi) (3-dimethylmino 2 methylpropyb propylammonium bromide, S-ester ester, 28.9 parts. with phosphorothiolc acid, O-phenyl es er.

The reaction is carried out 'as in Example 2'5'e'xcept th t 131' ture is refluxed 9 hrs.

35 Phosphorothioic acid; O-fillellyl, s- Dimethylsulfate, rat-parts; Benzene; 50 parts Diethyl (an mx eruyi ,methylam (2-diethylaminoethyl) ester, 28.9 monium methyl sulfate, S-es'ter with parts. phosphorothioic acid, 0-phenyl ester.

The reaction mixture is refluxed 30 min; The broduct is extracted with water, which is removed by distillation in vacuo 36..--.- Phosphorothioic ac d, ,G-(p-nitro- Methyl p tolu'enesulfonate, Benzene, 50 parts Diethyl (z-hrdroxyethyl) methylsmphenyl), S-(2-diethylaminoethyl) 18.6 parts. monium p-toluenesulfonate, S P5ter ester, 33.4 parts. w th phosophorothioic acid, O-(p mtrophenyl) ester.

The reaction mixture is stirred and heated at for 4 hrs. The benzene is removed by distillation in vacuo use of the compounds of the invention as insecticides.

EXAMPLE 45 Diethyl (Z-hydroxyethyl)methylammonium methyl sulfate, S-ester with phosphorothioic acid, O-butyl ester is admixed with percent by weight of a proprietary wetting, dispersing and emulsifying agent having as its efifective ingredient polyethylene oxide modified sorbitan monolaurate.

The formulation thus prepared is readily soluble in water to obtain aqueous spray compositions which are highly effective when applied to growing crops for the control of a wide variety of insects such as mites, aphids, southern armyworms, and onion thrips.

A spray composition suitable for application to fruit trees is prepared by dissolving 16 ounces of the formulation of this example in 100 gallons of water. This gives excellent control of mites, green apple aphids, scale insects and other insects when used in an orchard of mixed fruit species, that is, containing plum, peach, apple and cherry trees.

The spray composition described above also gives excellent control of insects including mites, aphids, and yellow-striped armyworms when applied to growing cotton plants in fields infested with these species.

Ex. N 0 Starting Material Quaternizing Agent Solvent Product 37 Phosphorodithioic acid, O-(ohloro- Propyl iodide, 34.0 parts Benzene, 50 parts Dimethyl (Z-hydroxyethyl) propylphenyl), S-(2-dimethy1aminoethyl) ammonium iodide, S-ester with ester, 31.2 parts. phosphorodithioic acid, O-(o-chlorophenyl) ester.

The reaction is carried out as in Example except that the mixture is refluxed 8 hrs.

38 Phosphorothioic acid, O-(o-tolyl), S tert.-Butyl benzenesnh'o- Toluene, 50 parts Dimethyl (Z-hydroxyethyl) tert.-buty1- (2-dimethylaminoethyl) ester, 27.5 nate, 21.4 parts. ammonium benzenesulfonate, S-ester parts. with phosphorothioic acid, O-(otolyl) ester.

The reaction mixture is heated 24 hrs. at 60. The toluene is removed by distillation in vacuo 39 Phosphorothioic acid, O-benzyl, S- Dimethyl sulfate, 12.6 parts. Diethyl ether, 60 parts Trimethyl (Z-hydroxyethyl) ammo- (2-dimethylaminoethyl) ester, 27.5 nium methyl sulfate, S-ester with parts. phosphorothioic acid, Q-benzyl ester.

The reaction mixture is shaken 24 hrs. at room temp. The ether is removed by evaporation in a stream of dry air 40 Phosphorodithioic acid, O-methyl, 8- Methyl p-toluenesulfonate, Diethyl ether, parts 1-.Methyl-1-(2-hydroxyethyl) pyrroli- [2-(l-pyrrolidino) ethyl] ester, 24.1 18.6 parts. dinium methyl sulfate, S-ester with parts. phosphorodithioic acid, O-methyl ester.

The reaction mixture is shaken 36 hrs. at room temp. The ether is removed by distillation in vacuo 41 Phosphorothioie acid, O-butyl, S-[3- Diethyl sulfate, 15.4 parts.-. N o solvent l-Ethyl-l-(3-hydroxypropyl) piperidin- (l-piperldino) propyl] ester, 29.5 ium ethyl sulfate, S-ester with phosparts. phorothioic acid, O-butyl ester.

The reactants are combined (no solvent) and heated 6 hrs. at

42 Phosphorothioic acid, O-ethyl,- S-[2- Methyl chloride, 6.30 parts N o solvent l-Methyl-l-(2-hydroxyethyl) pipera (l-piperazino) ethyl] ester, 25.4 zinium chloride, S-ester with phos parts. phorothioic acid, O-ethyl ester.

. The reaction is carried out as in Example 19 4s Phosphorodithioic acid, O-methyl, s- Ethyl iodide, 31.0 parts- No solvent l-Ethyl-l-(2hydroxyethyl) niorpholin- [Q-(l-morpholino) ethyl] ester, 25.7 ium iodide, S-ester with phosphor-v parts. odithioic acid, O-methyl ester.

The reaction is canied out as in Example 27 44 Phosphorodithioic acid, O-methyl, 8- Methyl bromide, 11.9 parts No solvent Methyl di-(2-methylallyl) (2-hydroxy- [2-di (2-methylallyl) aminoethyl] ethyl) ammonium bromide, S-ester ester, 29.5 parts. with phosphorodlthioic acid, 0-

methyl ester.

The reaction is carried out as in Example 21 The following examples illustrate the formulation and EXAMPLE 46 An insecticidal dust is prepared by admixing triisopropyl (Z-hydroxyethyl) ammonium bromide, S-ester with phosphorodithioic acid, O-ethyl ester with tale in the proportions of about 32 parts by'weight of talc for each part by A water-dispersible insecticidal powder is obtained by blending a compound of the invention with an adsorbent carrier, a diluent and surfactants in the following proportions by weight:

25% dipropyl (3-hydroxypropyl)ethylammonium iodide, S-ester with phosphorothioic acid, O-isopropyl ester 73% diatomaceous earth (adsorbent carrier and diluent) 1% low viscosity methylcellulose (dispersing agent) 1% cetyl trimethylammonium bromide (wetting agent) The following examples illustrate the outstanding in- V secticidal activity of the compounds of this invention.

EXAMPLE 48 In order to illustrate the systemic action of a typical compound of the invention, 100 ml. of a solution containing 0.005 percent by weight of diethyl (2-hydroxyethyl)methylamrnonium methyl sulfate, S-ester with phosphorothioic acid, O-ethyl ester was poured onto the soil surface in each of a number of four-inch clay pots containing two red kidney bean plants approximately 4 inches tall. The pots of beans were subsequently infested with two-spotted mites two, three and four days after treatment. Mortality counts of adults mites were made on the second day following the mite infestations. It was found that 60 percent of the mites applied two days after treatment were dead at the time the mortality count was made, 98 percent of the mites applied three days after treatment were dead at that time and 96 percent of the mites applied four days after treatment were dead at the time of mortality count.

EXAMPLE 49 This example illustrates the startling retention of insecticidal activity from foliar sprays.

Five-year old Golden Delicious apple trees were sprayed to the run-0E point with an aqueous solution containing /z ounce of the compound of Example 1 per 100 gallons of spray. Leaves of these trees were heavily infested with two-spotted mites prior to the spray application. Mortality counts of adults mites were made periodically following the spray application. It was found that excellent control (in excess of 98% mortality) was obtained for a period of 38 days, and that satisfactory control (in excess of 90% mortality) was obtained for76 days.

, EXAMPLE The'excellent contact action of the compounds of-this' EXAMPLE 51 The varied insecticidal activity of the compounds of 16 the invention is illustrated by other evaluations in which it was found, for example, that the compound of Example 1 when applied asa 2 percent aqueous solution effected l00percent kill of such. insects as adult housefly, German roach nymph, adult confused flower beetle, black carpet beetle larvae, adult granary weevil, and bean aphid.

The claims are:

1. Di'-O,S-hydrocarbon esters of phosphorothioic acid and phosphorodithioic acid represented by the formula where:

X is fselected from the group consisting of oxygen and sul or.

R is selected from the group consisting of alkyl radicals of from 1 to 4 carbon atoms, inclusive, alkenyl of 2 to 4 carbon atoms, benzyl, phenyl, halophenyl, nitrophenyl, and tolyl radicals.

R is an alkylene radical of 2 to 4 carbon atoms.

R; is selected from the group consisting of alkyl radicals of 1 to 4 carbon atoms, inclusive, and alkenyl radicals of 2 to 4 carbon atoms.

R and R are the same and are selected from the group consisting of alkyl radicals of 1 to 4 carbon atoms, in.- clusive, and alkenyl radicals of 2 to 4 carbon atoms, with the proviso that R; and R can be taken together to form, with the included nitrogen, a ring selected from the group consisting of pyrrolidine, piperidine, piperazine, and morpholine.

A is selected from the group consisting of halogen, alkyl sulfate of from 1 to 4 carbon atoms, inclusive, benzenesulfonate, and toluenesulfonate.

2. An insecticidal composition comprising, in an insecticidally effective amount, at least one compound described in claim 1, and an inert carrier.

3. An insecticidal composition according to claim 2 containing an insecticidally inert powder as a carrier.

4. An insecticidal composition according to claim 2 containing a surface-active dispersing agent as a carrier.

5. A method of controlling insects which comprises applying to the locus .to be protected, in an amount sulficient to exert insecticidal action, a compound described in claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 1,711,696 Schoeller et'al. May 7, 1929 2,006,227 Bousquet June 25, 1935 2,736,726 Gaetzi et a] Feb. 28, 1956 FOREIGN PATENTS 1,004,898 France Dec. 5, 1951 OTHER REFERENCES Baer at 211.: J. Am. Chem. Soc.'70, 13941399 (1948). 

1. DI-O,S-HYDROCARBON ESTERS OF PHOSPHOROTHIOIC ACID AND PHOSPHORODITHIOIC ACID REPRESENTED BY THE FORMULA
 2. AN INSECTICIDAL COMPOSITION COMPRISING, IN AN INSECTICIDALLY EFFECTIVE AMOUNT, AT LEAST ONE COMPOUND DESCRIBED IN CLAIM 1, AND AN INERT CARRIER. 